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111.
The technique of constant-potential electrolysis at a stationary spherical electrode (hanging mercury drop) was investigated for the determination of the diffusion coefficient of Tl(I) in sodium citrate-sodium hydroxide medium and of Tl in mercury. Current-time curves, at controlled potential, were obtained, covering periods from 1 to 25 sec after the start of the electrolysis. The influence of applied potential, time of electrolysis, convection and shielding of the electrode was studied. 相似文献
112.
Hans‐Ruedi Mürner Rosario Scopelliti Jean‐Claude G. Bünzli 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(8):m434-m435
In the title compound, [TbCl(C27H35N3)2(H2O)](ClO4)2·2C2H6O, the TbIII ion has a coordination number of eight, composed of two tridentate substituted‐terpyridine ligands, a water molecule and a bound Cl? anion. The first coordination shell can be described as a distorted bicapped trigonal prism. The dihedral angles between pyridine rings belonging to the same tpy ligand range from 5.2 (5) to 16.8 (5)°. 相似文献
113.
Several derivatization procedures with o-phthaldialdehyde-N-acetylcysteine (OPA-NAC) were compared for a rapid analysis of primary aliphatic short-chain monoamines in water samples by HPLC using a LiChorospher analytical separation column (100RP18 mm i.d., 5 μm). Both the solution and the solid-support assisted off-line derivatization on C18 SPE cartridges were inadequate options because of beginning degradation processes of the instable isoindol derivatives during their transfer to the analytical column. This problem was precluded with the on-column or solid-support assisted on-line derivatization. In the last mentioned procedure, the derivatization took place in a Hypersil C18 precolumn ( mm i.d., 30 μm) connected with an additional preconcentration step resulting in better detection limits (0.002-0.040 μg ml−1 requiring only 150 μl of water sample) than in the on-column procedure (0.08-0.16 μg ml−1). The improved sample handling, the better control of parameters affecting reaction rates, the fully automation of this method with only 10 min analysis time for each sample are further advantageous. The potential of the solid-support assisted on-line derivatization was outlined and applied to water samples from several sources. Recovery values near 100% were obtained. 相似文献
114.
Martinez Alvarez R Herrera Fernandez A Chioua M Ramiro Perez P Villalba Vilchez N Guzman Torres F 《Rapid communications in mass spectrometry : RCM》1999,13(24):2480-2488
Several 5,6-dialkyl-2,4-diarylpyrimidines were prepared and their electron ionization (EI) mass spectra reported. The benzylic cleavage takes place easily together with an important McLafferty rearrangement. The involvement of the nitrogen atom appears to be important in the fragmentation of 5-methyl-substituted pyrimidines. In contrast, the 6-methyl-substituted pyrimidines undergo benzylic cleavage without hydrogen transfer. Thus, the difference in the mass spectrometric behaviour allows the identification of these isomeric compounds which, in contrast, exhibit only small differences in their NMR spectra. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
115.
Jean BourguignonUlf Bremberg Georges DupasKristina Hallman Lars HagbergLaurent Hortala Vincent LevacherSerghey Lutsenko Emmanuel MacedoChristina Moberg Guy QuéguinerFredrik Rahm 《Tetrahedron》2003,59(48):9583-9589
Chiral pyridinooxazoline, quinolinooxazoline, bis(oxazolino)pyridine (pybox), and bisoxazoline (box) derivatives containing crown ether residues were prepared. Some of the ligands were assessed in substrate binding studies and in palladium catalyzed allylic alkylations. 相似文献
116.
Maria Fernanda Silva Estela Soledad Cerutti Luis D. Martinez 《Mikrochimica acta》2006,155(3-4):349-364
The purpose of this article is to review and evaluate cloud point extraction of metals and its coupling to different contemporary
instrumental methods of analysis. This review covers a selection of the literature published on this topic over the period
mainly between 1997 and September 2005 (consisting of 50 publications). The current state of the art for CPE concerning metals
and metal chelates is presented with special emphasis on the hyphenation of this interesting extraction/preconcentration approach
mediated by surfactants to spectrophotometry, atomic spectroscopy and separation techniques. We present contemporary CPE developments
concerning metal speciation and determination and their application to different environmental, clinical, geological and food
samples. Strategies for method development as well as future perspectives are also covered. 相似文献
117.
Regioselectivite de la reaction des dialkyl cuprates de magnesium sur des aldehydes α,β-ethyleniques
Monique Bourgain-Commerçon Jean-Pierre Foulon Jean François Normant 《Journal of organometallic chemistry》1982,228(3):321-326
Various magnesium organocuprates give conjugative addition products with α,β-ethylenic aldehydes, and even with acrolein. The enolates may be trapped with bromine or trimethylsilyl chloride. 相似文献
118.
The ultraviolet absorption spectrum of the neopentyl peroxy radical (CH3)3CCH2O2, and the kinetics and products of its self reaction have been studied in the gas phase at 298 K. Absorption cross sections were quantified over the wavelength range 230–290 nm. The measured cross section at 250 nm was; Errors represent statistical (2σ) together with our estimate of potential systematic errors(15%). The kinetics of the decay of the UV absorption following the generation of the neopentyl peroxy radicals was complicated by the rapid decomposition of the (CH3)3CCH2O radicals formed in channel (4a). By measuring the yield of t-butyl peroxy radicals, the branching ratio k4a/(k4a + k4b) was determined to be 0.39 ± 0.03. The rate constant for the self reaction of neopentyl peroxy radicals was k4 = (1.07 ± 0.22) × 10?12 cm3 molecule?1 s?1. Quoted errors represent 2σ. These results are discussed with respect to the available literature data. © John Wiley & Sons, Inc. 相似文献
119.
Jean -Paul Malrieu 《Theoretical chemistry accounts》1982,62(2):163-174
Using the canonical problem of N separate electron pairs, theN dependence of approximate multireference CI schemes is analyzed. When the DCI is taken as multireference space, the second order Quasi Degenerate Many Body Perturbation Theory (QD(MB)PT) gives twice the expected correction, while the CIPSI algorithm gives 66% of it, and the MRDCI a vanishing part of it. A modified QDPT effective hamiltonian, and a combination of CIPSI and QDPT algorithms seem to give better trends. 相似文献
120.
Synthesis, characterization and crystal structures of two polyphilic mesogenic compounds 总被引:1,自引:0,他引:1
Philippe Kromm Michel Cotrait Jean Claude Rouillon Philippe Barois Huu Tinh Nguyen 《Liquid crystals》1996,21(1):121-131
Three homologous series of semi-perfluorinated liquid crystals: 4-(2,2,3,3,4,4,4-heptafluoro-butyloxycarbonyl)phenyl, 4-(2,2,3,3,4,4,5,5-octafluoropentyloxycarbonyl)phenyl and 4-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxycarbonyl)phenyl 4-[(n-perfluoroalkyl)alkyloxy]benzoates have been synthesized. Their mesomorphic properties were studied by DSC, microscopic observation and X-ray diffraction. Their layer spacings are smaller than the molecular length (L). The ratio dSA/L is about 0.7. The crystal structure of two derivatives of the first family have also been investigated. In both structures the molecules pack in smectic C-like sheets where neighbouring molecules are antiparallel, interacting through dipolar and van der Waals forces. The interactions between contiguous sheets, through the ends of perfluorinated chains are very weak. The X-ray diffraction results on the mesophases and on the crystalline structures of two compounds of the first family are compared. From this, we propose a model of the smectic phases with a zig-zag structure. 相似文献